DE1072764B - Process for the production of azo dyes - Google Patents

Description

Process for the production of azo dyes Addendum to the patent 1 014 249 The subject of the patent 1 014 249 is a process for the production of azo dyes, which consists in using azo components of the general formula where R denotes an alkyl, aryl, cycloalkyl or aralkyl radical, with diazo, diazoazo or tetrxzo compounds which contain at least one sulfonic acid, carboxylic acid or oxy group, and optionally couples the azo dyes obtained in substance or on the fiber with metal donating Means treated.

According to this process, in which the azo components dioxyphenyl-alkyl-, -aryl-, -cycloalkyl- and -aralkylketones are used, azo dyes are obtained, which, depending on their structure, are used to dye fibers made from natural cellulose or Polyamides and animal materials such as wool or leather are suitable. The dyes can in substance, on the fiber or in the dyebath in the usual way with metal donors Agents, for example chromium, copper, cobalt, manganese, nickel or iron compounds, are treated, whereby the fastness of the underlying dyes is essential can be improved. The metal complex compounds are particularly valuable these dyes, which can be used to dye wool or leather, dyeings with very good fastness properties, especially on leather of very good light and wet fastness properties.

In pursuing this inventive concept, it has now been found that dyes with similarly good fastness properties are obtained if, in the process of the main patent, trioxy- or tetraoxymono- or diketones of the general formula are used as azo components where R is an alkyl or aryl radical, one X is a hydroxyl group, the other X is hydrogen or a hydroxyl group and n = 0 or 1 is used. The coupling can be carried out one to four times, in which case, depending on the type of diazo or tetrazo compounds, mono-, dis- or polyazo dyes are obtained.

As azo components which are used in the process according to the invention can reach, for example, the following may be mentioned 2,2 ', 4-trioxybenzophenone, 2,4,4'-trioxybenzophenone, 2,2 ', 4,4'-tetraoxybenzophenone, 2', 2 ", 4 ', 4" -tetraoxy-1,4-dibenzoylbenzene, M.p. 331 to 333 ° C, 2 ', 2 ", 4', 4" -Tetraoxy-1,4-dibenzoylbutane, mp 310 ° C.

The azo components can be prepared by known methods, for example by reacting carboxylic acid chlorides with 1,3-dioxybenzene under the conditions of the Friedel-Crafts reaction or by condensation of the free Carboxylic acids with 1,3-dioxybenzene under the action of boron trifluoride.

The present proceedings are, moreover, closely related to that of the main patent at.

The new dyes are those from German Patent 900 600 known dyes of similar composition in terms of lightfastness are essential think.

Example 23.4 parts by weight of 1-amino-2-oxy-3-nitrobenzene-5-sulfonic acid (0.1 mol) are stirred with 200 parts by volume of water and at 18 ° C. with 20 parts by volume of 5N sodium nitrite solution over the course of about one hour diazotized. The diazo solution is then combined with a solution of 23 parts by weight of 2,2 ', 4-trioxybenzophenone (0.1 mol) in 60 parts by volume of 5N sodium hydroxide solution and 60 parts by weight of water. After the coupling has ended, the mixture is acidified with acetic acid, most of the dye separating out. It is completely salted out with table salt, vacuumed and dried. The thus obtained dye of the formula is a dark brown powder which is easily soluble in water and which dyes wool in bluish garnet tones, which change into bordo tones during copper plating and reddish brown shades during re-chrome plating with good fastness properties, in particular very good lightfastness. To prepare the chromium complex compound of the above-mentioned dye, after the coupling has ended, it is acidified with acetic acid, heated, an aqueous solution of 25 parts by weight of chromium acetate containing 30.05% Cr 2 O 3 (0.1 mol) is added and a few more hours heated to 90 to 95 ° C. After the chromation has ended, the chromium-containing dye is salted out with common salt, filtered off with suction and dried. It is a dark brown powder that dissolves easily in water and dyes leather in bordeaux red shades of very good wet fastness and very good lightfastness.

The table below describes other azo dyes with similar fastness properties that can be obtained from 1 mole of an azo component and 1 to 4 moles of a diazo component in a manner similar to that described in the previous example, as well as their color shades on wool, polyamide fibers and leather . Hue on wool hue hue Diazo component @zo component on poly- the chromium-com- post-post plex connection (MO1) 1 mole untreated I chromed copper-plated carrion on leather 1-Amino-2-oxy-2,4,4'-Trioxybenzophenone Corinth Garnet Red-brown - Bordo 3 nitrobenzene-5-sul- fonsäure (1 mole) the same. (2 mol) the same. red-tinged garnet garnet - violet dark blue the same. (1 mol) 2,2 ', 4,4'-tetraoxybenzo-garnet red-brown red-brown medium-Bordo phenon brown the same. (2 mol) the same. Bordo dark red red-brown - Bordo the same (4 moles) the same - - - - Violet the same. (2 mol) 2,2 ', 4-trioxybenzophenone gray-brown dull red-tinged dark bordo Bordo blue brown - the same. (2 mol) 2 ', 2 ", 4', 4" -Tetraoxy-1,4-di-Wine red, red-brown, red-brown - Bordo benzoylbenzene 1-Amino-2-oxyben-2,2 ', 4-trioxybenzophenone red medium - Bordo red brown - red brown zol-5-sulfonic acid brown (i m01) the same. (2 mol) the same. red middle Bordo Bordo - bluish tint brown Bordo the same. (1 mol) 2,4,4'-trioxybenzophenone brownish-brownish yellowish-red-brown orange garnet brown - the same. (2 mol) the same. Scarlet garnet red-brown - Bordo the same. (1 mol) 2,2 ', 4,4'-tetraoxybenzo-orange bordo rust-brown yellow-brown bordo phenone the same (4 moles) the same rust brown garnet bordo brown bordo - the same. (2 mol) 2 ', 2 ", 4', 4" -Tetraoxy- yellow-brown red-brown medium brown - cloudy red 1,4-dibenzoylbenzene likewise (2 moles) 2 ', 2 ", 4', 4" -Tetraoxy- - - - - Violet 1,4-dibenzoylbutane 1-Amino 2-oxy-6-ni- 2,2 '; 4-Trioxybenzophenone Dark Corinth Dark Corinth Dark Gray tronaphthalin-4-sul brown red-brown fonsäure (1 mole) the same (2 mol) the same the same the same Bordo Corinth Black the same. (1 mol) 2,4,4'-trioxybenzophenone dull red-tinged- Bordo garnet blue-tinged- Dark black black - blue -- the same (2 mol) the same dark- red-tinged- wine red Corinth blue-tinged- brown gray black the same. (1 mol) 2; 2 ', 4,4'-tetraoxybenzo- dark red-brown rust-red red-brown dark brown phenon brown Diazo component Azo component shade on wool shade shade on poly- the chromium- post-post plex connection (Mo1) 1 mole untreated chromed I copper-plated amide fiber on leather the same. (4 mol) the same. - - - - Black the same. (2 mol) 2 ', 2 ", 4', 4" -Tetraoxy- Bordo red-brown wine-red - dark- 1,4-dibenzoylbenzene red-brown, 1-Amino-2-oxy-2,2 ', 4-trioxybenzophenone Light brown Bordo Bordo Red brown Bordo 5-chlorobenzene-3-sul- fonsäure (1 mole) the same. (2 mol) the same. Medium brown Medium brown Wine red - violet the same. (1 mol) 2,4,4'-trioxybenzophenone - garnet dull yellowish bordo Red brown the same. (2 mol) the same. Rust brown garnet garnet brown-violet stitch red the same. (2 moles) 2 ', 2 ", 4', 4" -Tetraoxy- yellow-brown Corinth yellow-brown - Bordo 1,4-dibenzoylbenzene 1-aminobenzene-2,2 ', 4-trioxybenzophenone light reddish yellow-brown - yellow-brown 2-carboxylic acid yellow-brown 3-medium 4-sulfonic acid (1 mol) brown. the same. (1 mol) 2,4,4'-trioxybenzophenone orange rust brown yellow brown muted red brown orange the same (2 mol) the same orange rust brown yellow brown orange red brown 1-Amino-2-oxyben- 2 ', 2 ", 4', 4" -Tetraoxy- Brown Corinth Red Brown - Red Brown zene-3-carboxylic acid 1,4-dibenzoylbenzene 5-sulfonic acid (2Mo1) The following compilation = contains a number of further azo dyes obtainable according to the invention with similarly good fastness properties, which can be produced from 1 mol of an azo component and 2 to 4 mol of a diazo component and subsequent chromating, as well as their color shades on leather. Diazo component Azo component hue (Moles) 1M01 on leather 1-Amino-2-oxy-5-chlorobenzene-3-sulfonic acid (2 moles) 2,2 ', 4,4'-tetraoxybenzophenone violet the same (4 moles) the same violet 1-aminobenzene-2-carboxylic acid-4-sulfonic acid (2 moles) 2,2 ', 4-trioxybenzophenone light brown 1-aminobenzene-2-carboxylic acid-5-sulfonic acid (2 mol), same medium brown likewise (2 moles) 2 ', 2 ", 4', 4" -Tetraoxy-1,4-dibenzoylbutane Medium brown 1-Amino-2-oxy-3-chlorobenzene-5-sulfonic acid (2 moles) 2,2 ', 4-trioxybenzophenone Bordo the same. (2 mol) 2,2 ', 4; 4'-tetraoxybenzophenone red-brown 1-Amino-2-oxy-5-nitrobenzene-3-sulfonic acid (2 mol) also red-brown 1-Amino-2-oxynaphthalene-4-sulfonic acid (2 mol) the same red-tinged black 1-aminobenzene-2-carboxylic acid-5-sulfonic acid (4 mol) the same red-brown Diazo component I Diazo component II Azo component Color shade on leather 1-aminobenzene-2-carboxylic acid-5-sulfone-1-amino-4-nitrobenzene-2-sul-2,2 ', 4,4'-tetraoxy- medium brown acid (2 moles) fonsäure (2 moles) benzophenone 1-Amino-2-oxy-3-nitrobenzene-5-sulfone like (2 mol) like cloudy Bordo acid (2 mol) 1-Amino-2-oxy-5-chlorobenzene-3-sulfone- like (2 mol) like red-brown acid (2 mol) 1-Amino-2-oxy-3,5-dinitrobenzene 1-aminobenzene-2-carbon- like olive gray alkaline acid-4-sulfonic acid (1 mol) 1-amino-8-oxynaphthalene-3,6-disulfone acid (1 mole)

Claims (1)

PATENT CLAIM: Modification of the process for the preparation of azo dyes according to patent 1 014 249, characterized in that the azo components used here are trioxy- or tetraoxymono- or diketones of the general formula where R is an alkyl or aryl radical, one X is a hydroxyl group, the other X is hydrogen or a hydroxyl group and n = 0 or 1 is used. Documents considered: German Patent No. 900 600; Liebigs Annalen der Chemie, Vol. 329 [1903], p.278. When the application was announced, 1 staining table with an explanation was laid out.